DSE Chem notes (Rate equation)

Chapter 51 – Rate equation

51.1 Reaction rate
- The progress of a chemical reaction can be represented by a concentration-time graph.

- Instantaneous rate is the rate at a particular instant of the reaction. It is found by drawing a
tangent to the concentration-time curve at that particular instant.

- Initial rate is the instantaneous rate at the start of the reaction. It is found by drawing a
tangent to the concentration-time curve at time zero.

- Initial rate is important in the study of chemical kinetics because the initial ______________ of
the ____________ are known.

- Unit of reaction rate : _____________

51.2 Rate equation and order of reaction

- A rate equation (also known as rate law) shows the quantitative relationship between the
rate of reaction and the concentration of the reactants.

- Rate equations are deduced from __________________ results.

e.g. 2N2O5(g) 
 4NO2(g) + O2(g)

The graph shows that the reaction rate is

directly proportional to the concentration
of N2O5(g).
Rate [N2O5(g)]
Rate = k [N2O5(g)]

This is known as the rate equation and

‘k’ is known as the rate constant of the reaction.

- In general, for a rate equation

Rate = k [A]x [B]y

k is the rate constant (x + y) is the overall order of reaction

x is the order of reaction with respect to A (x and y are usually integers, but can also be
y is the order of reaction with respect to B fractions)
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DSE Chem notes (Rate equation)
Rate constant
- Rate constant is a proportionality constant in the rate equation.

- A larger k indicates a ____________ reaction rate.

- Value of k ____________ with increase in temperature but is independent of concentrations

of reactants.

- Unit of k varies according to the overall order of reaction.

Rate equation Overall order Reaction type Unit of k

Rate = k [A]0 0 Zeroth order reaction

Rate = k [A] 1 First order reaction

Rate = k [A]2 / Rate = k [A][B] 2 Second order reaction

Zeroth Order Reaction

- Rate of reaction is ______________ of concentration of reactants.

- Rate remains ____________ throughout the reaction.

- Rate = k[reactant]0
∴ Rate = k
Rate / mol dm-3 s-1
[A] / mol dm-3

Time / s [A] / mol dm-3

Rate = k (unit of k : mol dm-3 s-1)

e.g. Decomposition of ammonia on hot platinum surface.

Pt
2NH3(g) 
 N2(g) + 3H2(g)

When the platinum surface is saturated with ammonia molecules, increase in concentration
of ammonia cannot increase the reaction rate further.

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DSE Chem notes (Rate equation)
First Order Reaction
- Rate of reaction is directly _______________ to concentration of reactant.

- As reaction proceeds, concentration of reactant ____________, rate of reaction also

_____________.

Rate / mol dm-3 s-1

[A] / mol dm-3

Time / s [A] / mol dm-3

Rate = k [A] (unit of k : s-1 )

e.g. SO2Cl2(l) SO2(g) + Cl2(g) Rate = k [SO2Cl2(l)]

(CH3)3CCl(l) + OH-(aq) (CH3)3COH(l) + Cl-(aq) Rate = k[(CH3)3CCl(l)]

Second Order Reaction

- Rate of reaction is proportional to the square of concentration of one reactant or directly
proportional to the concentration of each of the two reactants.
Rate / mold m-3 s-1

Rate / mold m-3 s-1

Rate / mold m-3 s-1

[A] / mol dm-3 [B] / mol dm-3

[A]2 / mol2 dm-6 ([B] is kept constant) ([A] is kept constant)

Rate = k [A]2
or Rate = k [A][B] (unit of k : mol-1 dm3 s-1)

e.g.
2NO2(g) 
 2NO(g) + O2(g) Rate = k [NO2(g)]2

CH3Br(l) + OH-(aq) 
 CH3OH(l) + Br-(aq) Rate = k [CH3Br(l)][OH-(aq)]

H+
CH3COCH3(aq) + I2(aq) 
 CH3COCH2I(aq) + HI(aq) Rate = k [CH3COCH3(aq)][H+(aq)]

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DSE Chem notes (Rate equation)
51.3 Finding order of reaction from initial rates
Graphical method
- Carry out the reaction several times, varying the initial concentration of reactant.
e.g. MnO2(s)
H2O2(aq)  2H2O(l) + O2(g)

- Find the initial rates from the concentration-time graph by drawing tangents to the curves at
time zero.

- Plot a suitable graph of ________ _______ against _________ ____________ of reactant.

Zeroth order First order Second order

Rate

Rate

Rate

[reactant] [reactant] [reactant]2

- If the rate is constant, irrespective of [reactant], the order of reaction is ____.

- If a plot of rate against [reactant] gives a straight line, the order of reaction is ____.

- If a plot of rate against [reactant]2 gives a straight line, the order of reaction is ______.

Alternative graphical method

- This method is especially useful for reactions with a fractional order.

- Take logarithm of the rate equation:

log[reactant]
x
Rate = k [reactant]

log (rate) = x log [reactant] + log k

log (rate)

- Plot a graph of log(rate) against log[reactant]

(Slope of the straight line = x ;

y-intercept = log k)

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DSE Chem notes (Rate equation)
Numerical method
- Carry out a reaction several times, using different initial concentrations of reactants and then
measure the initial rates.

- By comparing the changes in concentration and reaction rates, the order of reaction can be
deduced.
e.g. For the reaction between potassium iodide (KI) and potassium peroxodisulphate (K2S2O8),
the following results were obtained from experiment.
Initial concentration / mol dm-3 Initial rate /
Trial
[S2O82-(aq)] -
[I (aq)] 10-6 mol dm-3 s-1

1 0.038 0.030 7.0

2 0.076 0.030 14.0
3 0.076 0.060 28.0

Comparing trials (1) and (2):

When [S2O82-(aq)] is doubled, rate is also ___________
∴ the reaction is ________ order with respect to S2O82-(aq)

(OR the order of reaction with respect to S2O82-(aq) is 1)

Comparing trials (2) and (3):

When [I-(aq)] is doubled, rate is also ___________
∴ the reaction is ________ order with respect to I-(aq)

(OR the order of reaction with respect to I-(aq) is 1)

The rate equation for the reaction is:

Rate =

Alternative method (useful for fractional orders)

Let the rate equation be:
Rate = k [S2O82-(aq)]x [I-(aq)]y

Comparing trials (1) and (2):

14.0  10 -6 k( )x ( )y

7.0  10 -6 k( )x ( )y
(0.076) x
2
(0.038) x

x = ______

∴ the reaction is ________ order with respect to S2O82-(aq)

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DSE Chem notes (Rate equation)
Comparing trials (2) and (3):

28.0  10 -6 k( )x ( )y

14.0  10 -6 k( )x ( )y
(0.06) y
2
(0.03) y

y = ______

∴ the reaction is ________ order with respect to I-(aq)

The rate equation for the reaction is: Rate =

Work example
An acidic solution containing iodate ions, IO3-(aq), reacts with KI(aq) as shown in the following
equation.
IO3-(aq) + 6H+(aq) + 5I-(aq) 
 3I2(aq) + 3H2O(l)

An experiment was done to determine the rate of formation of iodine. The results were recorded in
the table below:
Initial [IO3-(aq)] Initial [I-(aq)] Initial [H+(aq)] Rate of formation of I2(aq)
Trial
/ mol dm-3 / mol dm-3 / mol dm-3 / 10-6 mol dm-3s-1
1 0.0001 0.0001 0.0001 0.5
2 0.0002 0.0001 0.0001 1.0
3 0.0001 0.0003 0.0001 1.5
4 0.0001 0.0003 0.0002 6.0
5 0.0002 0.0004 0.0001 ?

(a) Deduce the rate equation of the above reaction.

(b) Calculate the rate constant of the reaction.
(c) What will be the rate of formation of iodine in trial 5?
(d) What is the rate of disappearance of I-(aq) in trial 4?

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DSE Chem notes (Rate equation)
Appendix

Measuring initial rates experimentally

Since reaction rate is inversely proportional to the reaction time, initial rate can be determined by
measuring the time taken for the formation of a small amount of product.

(A) Measure the time for the formation of a small amount of a precipitate

S2O32-(aq) + 2H+(aq) 
 SO2(g) + H2O(l) + S(s)

- Put the thiosulphate solution in a beaker.

- Place the beaker over an ‘X’ marked on a white tile.
- Add dilute acid into the beaker and start the stop watch.
- Record the time(t) taken for the ‘X’ to disappear from sight (it is the time required for the
formation of a small amount of sulphur precipitate).
- 1/t can then be used to represent the __________ ________ of the reaction.

1
Initial rate α
time taken for the cross to disappear

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DSE Chem notes (Rate equation)

(B) Clock reaction

- A clock reaction is characterized by a sharp ____________ change after an induction

period, due to an increase in concentration of a certain chemical species.
- Iodine clock reaction is commonly used to study rates of reactions.

H2O2(aq) + 2I-(aq) + 2H+(aq) 

 I2(aq) + 2H2O(l) main reaction

- A small and fixed amount of S2O32-(aq) and some starch indicator are added to the reaction
mixture. The __________ formed will be consumed immediately by the thiosulphate
according to the following equation:

2S2O32-(aq) + I2(aq) 
 S4O62-(aq) + 2I-(aq) monitor reaction

- Once the S2O32-(aq) is used up, any free iodine present will form a dark ________ complex
with the starch indicator.

I2(aq) + starch 
 dark blue complex indicator reaction

- The time (t) needed for the dark blue colour to appear is the time required for the formation
of a small and fixed amount of iodine.

- 1/t can then be used to represent the __________ ________ of the reaction.

1
Initial rate α
time taken for appearance of a dark blue colour

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DSE Chem notes (Rate equation)

Following the course of a single reaction

Rather than doing a whole set of initial rate experiments, you can also get information about orders
of reaction by following a particular reaction from start to finish.
There are two different ways you can do this. You can take samples of the mixture at intervals and
do titrations to find out how the concentration of one of the reagents is changing. Or (and this is
much easier!) you can measure some physical property of the reaction which changes as the reaction
continues - for example, the volume of gas produced.
We need to look at these two different approaches separately.

Sampling the reaction mixture

Bromoethane reacts with sodium hydroxide solution as follows:

During the course of the reaction, both bromoethane and sodium hydroxide will get used up.
However, it is relatively easy to measure the concentration of the sodium hydroxide at any one time
by doing a titration with some standard acid - for example, with hydrochloric acid of a known
concentration.
You start with known concentrations of sodium hydroxide and bromoethane, and usually it makes
sense to have them both the same. Because the reaction is 1:1, if the concentrations start the same as
each other, they will stay the same as each other all through the reaction.
So all you need to do is to take samples using a pipette at regular intervals during the reaction, and
titrate them with standard hydrochloric acid in the presence of a suitable indicator.
That is a lot easier said than done!
The problem is that the reaction will still be going on in the time it takes for you to do the titration.
And, of course, you only get one attempt at the titration. By the time you take another sample, the
concentration of everything will have changed!

There are two ways to improve this.

You can slow the reaction down by diluting it, adding your sample to a larger volume of cold water
before you do the titration. Then do the titration as quickly as possible. That's most effective if you
are doing your reaction at a temperature above room temperature. Cooling it as well as diluting it
will slow it down even more.
But if possible (and it is possible in the case we are talking about) it is better to stop the reaction
completely before you do the titration.
In this case, you can stop it by adding the sample to a known volume (chosen to be an excess) of
standard hydrochloric acid. That will use up all the sodium hydroxide in the mixture so that the
reaction stops.

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DSE Chem notes (Rate equation)

Now you would back titrate the resulting solution with standard sodium hydroxide solution, so that
you can find out how much hydrochloric acid is left over in the mixture.
That lets you calculate how much was used up, and so how much sodium hydroxide must have been
present in the original reaction mixture.

Processing the results

You will end up with a set of values for concentration of (in this example) sodium hydroxide against
time. The concentrations of the bromoethane are, of course, the same as these if you started with the
same concentrations of each reagent.
You can plot these values to give a concentration-time graph which will look something like this:

You need to find the rates of reaction at a number of points on the graph, and you do this by drawing
tangents to the graph, and measuring their slopes.
You would then draw up a simple table of rate against concentration.
The quickest way to go on from here is to plot a log graph as described further up the page. You
would convert all your rates into log(rate), and all the concentrations into log(concentration). Then
plot log(rate) against log(concentration).
The slope of the graph gives you the order of reaction.
In our example of the reaction between bromoethane and sodium hydroxide solution, the order
would turn out to be 2.
Notice that this is the overall order of the reaction - not just the order with respect to the reagent
whose concentration you were measuring. The rate of reaction was falling because the concentrations
of both of the reactants were falling.

Note: This all takes ages to do - not just the practical which would probably take at least an hour, but all the graph
drawing, and processing the results from the graphs. There is no obvious way this could be asked in any normal
practical or written exam at this level.
I can see that it is just possible that you might be asked in principle how you would do it.

Following the course of the reaction using a physical property

An example where a gas is given off

A familiar example of this is the catalytic decomposition of hydrogen peroxide that we have already
looked at above as an example of an initial rate experiment.

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DSE Chem notes (Rate equation)
This time, you would measure the oxygen given off using a gas syringe, recording the volume of
oxygen collected at regular intervals.
So the practical side of this experiment is straightforward, but the calculation isn't.

The problem is that you are measuring the volume of product, whereas to find an order of reaction
you have to be working in terms of the concentration of the reactants - in this case, hydrogen
peroxide.
That means that you will have to work out the concentration of hydrogen peroxide remaining in the
solution for each volume of oxygen you record. To do this, you have to be happy with calculations
involving the ideal gas law (Out of syllabus) and also basic mole calculations.
Having got a table of concentrations against time, you will then process them in exactly the same
way as I described above. Plot the graph, draw tangents to find rates at various concentrations, and
then plot a log graph to find the order.

Note: It seems unlikely that you could ever be asked to do this in an exam situation. And, at this level, you would almost
certainly be given some guidance with the calculations
If you know that you can follow the course of a reaction which produces a gas using this method, that is probably
all you will need. But check our syllabus, and past papers and mark schemes.

Colorimetry
In any reaction involving a coloured substance (either reacting or being produced), you can follow
the course of the reaction using a colorimeter.

All of this is contained in one fairly small box.

The colour of the light can be changed by selecting a particular coloured filter (or using some more
sophisticated device like a diffraction grating). The colour is chosen so that it is the frequency of
light which is absorbed by the sample.
Taking copper(II) sulphate solution as a familiar example, you would choose to use a red filter,
because copper(II) sulphate solution absorbs red light. The more concentrated the solution is, the
more of the red light it will absorb.

Note: For an explanation of why absorbing red light makes copper(II) sulphate solution blue, see the note about the
transition metal. You don't need to read about the origin of the colour for now.

A commonly quoted example of the use of colorimetry in rates of reaction is the reaction between
propanone and iodine in the presence of an acid catalyst.

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DSE Chem notes (Rate equation)
The solution of iodine in propanone starts off brown, and then fades through orange to yellow to
colourless as the iodine is used up.
A colorimeter lets you measure the amount of light which is absorbed as it passes through a solution
- recorded as the absorbance of the solution.
It is common to plot a calibration curve for a colorimeter by making up solutions of the coloured
substance of known concentration and then measuring the absorbance of each under the same
conditions as you will do the experiment. You then plot a graph of absorbance against concentration
to give your calibration curve.
During your rate of reaction experiment, you read the absorbance from the meter at regular intervals,
and then use your calibration curve to convert those values into concentrations.
Then you are faced with the same graphical methods as before.

Note: In truth, these days, you are more likely to plug your colorimeter into a computer with the right software to do it all
for you!

pH measurements
If you have a reaction in which hydrogen ions are reacting or being produced, in principle you should
be able to follow changes in their concentration using a pH meter.
You may be aware that pH is a measure of hydrogen ion concentration, and it isn't difficult to
calculate an actual hydrogen ion concentration from a pH.
However, if you are measuring pH over a fairly narrow range of hydrogen ion concentrations, the pH
doesn't change all that much.
For example, the pH of a solution containing 0.2 mol dm-3 H+ has a pH of 0.70. By the time that the
concentration has fallen to 0.1 mol dm-3, the pH has only increased to 1.00.
Whether it is feasible to use a pH meter obviously depends on how accurate it is. If the pH meter
only recorded to 0.1 pH units, your results aren't going to be very good.

Conductivity measurements
The electrical conductivity of a liquid depends on the number of ions present, and the nature of the
ions. For example, we looked at this reaction much further up the page:

During the course of the reaction, as hydrogen ions and iodide ions get used up, the conductivity of
the mixture will fall.

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